The present invention relates to aqueous wood stains and to their use in a process for the staining of wood.
Stained woods, or the dyes applied to the wood often exhibit undesired bleaching or changes in shade as a result of the action of light and/or heat. Furthermore, the stained woods often display a colour unlevelness.
The use of solvent-containing wood stains for the photochemical and thermal stabilization of the (unstained) material wood is known, for example, from EP-A-0 943 665.
EP-A-0 479 075 discloses the treatment of wood with a wood stain comprising a colorant, a solvent and a stabilizer.
There continues to be a need for an improved protection of the stained wood against light and evolution of heat, and for a process which permits even penetration of the wood and uses low-solvent or solvent-free wood stains.
The object of the present invention was therefore to provide a process according to which the stained wood would satisfy today""requirements with regard to penetration, photostability and heat stability.
It has now been found that using the special wood stains described below it is possible to achieve good penetration and very good stabilization of stained wood.
Accordingly, the present invention provides a process for the staining of wood, which comprises treating the unstained wood with an aqueous preparation (stain) comprising
a) at least one dye and
b) at least one dye stabilizer of the formulae (I) or (II) 
xe2x80x83in which
G1 and G2, independently of one another, are C1-C4alkyl or together are pentamethylene,
Z1 and Z2 are methyl, or Z1 and Z2 form a bridging member which is unsubstituted or substituted by an ester, ether, hydroxyl, oxo, cyanohydrin, amido, amino, carboxyl or urethane radical,
E is oxyl or hydroxyl, and
X is an inorganic or organic anion, and
the total number of cations h corresponds to the total number of anions j.
Preference is given to dye stabilizers of the formulae (I) and (II) in which Z1 and Z2 are methyl or a bridging member containing 1-200 carbon atoms and 0-60 oxygen and/or nitrogen atoms.
X is, for example, phosphate, carbonate, bicarbonate, nitrate, chloride, bromide, bisulfite, sulfite, bisulfate, sulfate, borate, carboxylate, alkylsulfonate, arylsulfonate or phosphonate, for example diethylenetriaminepentamethylenephosphonate.
X as carboxylate is, in particular, a formate, acetate, benzoate, citrate, oxalate, tartrate, acrylate, polyacrylate, fumarate, maleate, itaconate, glycolate, gluconate, malate, mandalate, tiglate, ascorbate, polymethacrylate, nitrilotriacetate, hydroxyethylethylenediaminetriacetate, ethylenediaminetetraacetate or diethylenetriaminepentaacetate.
X is preferably chloride, bisulfite, bisulfate, sulfate, phosphate, nitrate, ascorbate, acetate, citrate, ethylenediaminetetraacetate or diethylenetriaminepentaacetate;
X is particularly preferably bisulfate or citrate.
h and j are preferably 1-5.
As a bridging member, Z1 and Z2 preferably contain 2 or 3 carbon atoms or 1 or 2 carbon atoms and a nitrogen or oxygen atom which together with the radical of the formulae (I) or (II) form a 5-membered or 6-membered heterocyclic ring which may be further substituted. The substituents of Z1 and Z2 can also contain radicals of sterically hindered amines. Preference is given to compounds of the formulae (I) and (II) containing 1-4, in particular 1 or 2, sterically hindered amines or sterically hindered ammonium radicals. Aryl is to be understood as meaning, for example, C6-C12aryl, in particular phenyl or naphthyl, especially phenyl.
The dye stabilizers given under b) can be used individually or as mixtures with one another.
Alkyl is to be understood as meaning, for example, C1-C18alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl or octadecyl.
Alkylene is to be understood as meaning, for example, methylene, 1,2-ethylene, 1,1-ethylene, 1,3-propylene, 1,2-propylene, 1,1-propylene, 2,2-propylene, 1,4-butylene, 1,3-butylen, 1,2-butylene, 1,1-butylene, 2,2-butylene, 2,3-butylene, or xe2x80x94C5H10xe2x80x94, xe2x80x94C6H12xe2x80x94, xe2x80x94C7H14xe2x80x94, xe2x80x94C8H16xe2x80x94, xe2x80x94C9H18xe2x80x94, xe2x80x94C10H20xe2x80x94, xe2x80x94C11H22xe2x80x94, xe2x80x94C12H24xe2x80x94, xe2x80x94C13H26xe2x80x94, xe2x80x94C14H28xe2x80x94, xe2x80x94C15H30xe2x80x94, xe2x80x94C16H32xe2x80x94, xe2x80x94C17H34xe2x80x94 and xe2x80x94C18H36xe2x80x94.
Cycloalkyl or cycloalkoxy are to be understood as meaning, for example, C5-C12-cycloalkyl or C5-C12-cycloalkoxy, such as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl or cyclododecyl, cyclopentoxy, cycloheptoxy, cyclodecyloxy or cyclododecyloxy.
Cycloalkenyl is to be understood as meaning, for example, C5-C12cycloalkenyl, such as cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl or cyclononenyl.
Aralkyl and aralkoxy are preferably phenylalkyl or phenylalkoxyl, such as benzyl, benzyloxy, xcex1-methylbenzyl, xcex1-methylbenzyloxy, cumyl or cumyloxy.
Alkenyl radicals are, for example, C2-C18alkenyl, in particular allyl.
Alkynyl radicals are, for example, C2-C12alkynyl, in particular propargyl.
Acyl is, for example, a radical R(Cxe2x95x90O)xe2x80x94, in which R is an aliphatic or aromatic radical.
Aliphatic or aromatic radical means, for example, an aliphatic or aromatic C1-C30hydrocarbon; for example aryl, alkyl, cycloalkyl, alkenyl, cycloalkenyl, bicycloalkyl, bicycloalkenyl, and a combination of these radicals.
Examples of acyl are C2-C12alkanoyl, C3-C12alkenoyl and benzoyl.
Examples of alkanoyl are formyl, propionyl, butyryl, pentanoyl, octanoyl and, in particular, acetyl.
Alkenoyl is preferably acryloyl or methacryloyl.
The alkyl substituents may be linear or branched.
Examples of C1-C6alkyl are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl and hexyl.
Examples of C2-C4alkenyl are ethenyl, propenyl and butenyl.
Examples of C1-C4alkyl which is interrupted by one or two oxygen atoms are xe2x80x94CH2xe2x80x94Oxe2x80x94CH3, xe2x80x94CH2xe2x80x94CH2xe2x80x94Oxe2x80x94CH3, xe2x80x94CH2xe2x80x94CH2xe2x80x94Oxe2x80x94CH2xe2x80x94CH3, xe2x80x94CH2xe2x80x94Oxe2x80x94CH2CH2xe2x80x94Oxe2x80x94CH3 and xe2x80x94CH2xe2x80x94Oxe2x80x94CH2xe2x80x94Oxe2x80x94CH3.
Preference is given to the dye stabilizers given under b) chosen from the compounds A to EE and A* to EE* and III to IIIc 
in which
E is oxyl or hydroxyl,
R is hydrogen or methyl,
in the formulae A and A*,
n is 1 or 2,
if n is 1,
R1 is hydrogen, C1-C18alkyl, C2-C18alkenyl, propargyl, glycidyl, C2-C50alkyl which is unsubstituted or substituted by one to ten hydroxyl groups and which may be interrupted by one to twenty oxygen atoms, or
R1 is C1-C4alkyl substituted by carboxyl or xe2x80x94COOZ, in which Z is hydrogen, C1-C4alkyl or phenyl or in which Z is C1-C4alkyl substituted by xe2x80x94(COOxe2x88x92)nMn+, in which n is a number 1-3 and M is a metal ion from the first, second or third group of the Periodic Table or is Zn, Cu, Ni or Co, or M is a group Nn+(R2)4, in which R2 is C1-C8alkyl or benzyl,
if n is 2,
R1 is C1-C12alkylene, C4-C12alkenylene, xylylene or C1-C50alkylene which is unsubstituted or substituted by one to ten hydroxyl groups and which may be interrupted by one to twenty oxygen atoms,
in the formulae B and B*,
m is 1 to 4,
if m is 1,
R2 is C1-C18alkyl, C3-C18alkyl interrupted by xe2x80x94COOxe2x80x94, C3-C18alkyl substituted by COOH or COOxe2x80x94, or R2 is xe2x80x94CH2(OCH2CH2)nOCH3, in which n is a number from 1 to 12, or R2 is C5-C12cycloalkyl, C6-C12aryl which is unsubstituted or is substituted by one to four C1-C4alkyl, or
R2 is xe2x80x94NHR3, in which R3 is C1-C18alkyl, C5-C12cycloalkyl, C6-C12aryl which is unsubstituted or is substituted by one to four C1-C4alkyl, or
R2 is xe2x80x94N(R3)2, in which R3 is C1-C18alkyl, C5-C12cycloalkyl, C6-C12aryl which is unsubstituted or is substituted by one to four C1-C4alkyl,
if m is 2,
R2 is C1-C12alkylene, C4-C12alkenylene, xylylene, C2-C12alkylene interrupted by xe2x80x94COOxe2x80x94, C3-C18alkylene substituted by COOH or COOxe2x80x94, or R2 is xe2x80x94CH2(OCH2CH2)nOCH2xe2x80x94, in which n is a number from 1 to 12, or
R2 is C5-C12cycloalkylene, C7-C15aralkylene or C6-C12arylene, or
R2 is xe2x80x94NHR4NHxe2x80x94, in which R4 is C2-C18alkylene, C5-C12cycloalkylene, C8-C15aralkylene or C6-C12arylene, or
R2 is xe2x80x94N(R3)R4N(R3)xe2x80x94, in which R3 and R4 are as defined above, or
R2 is xe2x80x94COxe2x80x94 or xe2x80x94NHxe2x80x94COxe2x80x94NHxe2x80x94,
if m is 3,
R2 is C3-C8alkanetriyl or benzenetriyl, or
if m is 4,
R2 is C5-C8alkanetetrayl or benzenetetrayl,
in the formulae C and C*,
R10 is hydrogen, C1-C18alkyl, C5-C12cycloalkyl, C7-C15aralkyl, C2-C18alkanoyl, C3-C5alkenoyl or benzoyl,
x is 1 or 2,
if x is 1,
R11 is hydrogen, C1-C18alkyl, C2-C18alkenyl, propargyl, glycidyl, C2-C50alkyl which is unsubstituted or substituted by one to ten hydroxyl groups and which may be interrupted by one to twenty oxygen atoms, or
R11 is C1-C4alkyl which is substituted by carboxyl or xe2x80x94COOZ, in which Z is hydrogen, C1-C4alkyl or phenyl, or in which Z is C1-C4alkyl which is substituted by xe2x80x94(COOxe2x88x92)nMn+, in which n is a number from 1-3, and M is a metal ion from the first, second or third group of the Periodic Table or is Zn, Cu, Ni or Co, or M is a group Nn+(R2)4, in which R2 is hydrogen, C1-C8alkyl or benzyl, or
if x is 2,
R11 is C1-C12alkylene, C4-C12alkenylene, xylylene, or C1-C50alkylene which is unsubstituted or is substituted by one to ten hydroxyl groups and which can be interrupted by one to twenty oxygen atoms,
in the formulae D and D*,
R10 has the meaning given above,
y is a number from 1 to 4, and
R12 has the meaning of R2,
In the formulae E and E*,
k is 1 or 2,
if k is 1,
R20 and R21, independently of one another, are C1-C12alkyl, C2-C12alkenyl or C7-C15aralkyl, or
R20 is hydrogen, or R20 and R21 are together C2-C8alkylene which can be substituted by hydroxyl, or C4-C22acyloxyalkylene or
if k is 2,
R20 and R21 are together (xe2x80x94CH2)2C(CH2xe2x80x94)2,
in the formulae F and F*,
R30 is hydrogen, C1-C18-alkyl, benzyl, glycidyl or C2-C6-alkoxyalkyl,
g is 1 or 2,
if g is 1,
R31 has the meaning of R1 if n is 1,
if g is 2,
R31 has the meaning of R1 if n is 2,
in the formulae G and G*,
Q1 is xe2x80x94NR41 or xe2x80x94Oxe2x80x94,
E1 is C1-C3alkylene, or E1 is xe2x80x94CH2xe2x80x94CH(R42)xe2x80x94Oxe2x80x94, in which R42 is hydrogen, methyl or phenyl, or
E1 is xe2x80x94(CH2)3xe2x80x94NHxe2x80x94 or E1 is a direct bond,
R40 is hydrogen or C1-C18alkyl,
R41 is hydrogen, C1-C18alkyl, C5-C12cycloalkyl, C7-C15aralkyl, C6-C10aryl, or R41 is xe2x80x94CH2xe2x80x94CH(R42)xe2x80x94OH, in which R42 is as defined above,
in the formulae H and H*,
p is 1 or 2,
T4 has the meaning of R11 if x is 1 or 2,
M and Y, independently of one another, are methylene or carbonyl, where M is, in particular, methylene and Y is carbonyl,
in the formulae I and I*,
these formulae are a repeating structural part of a polymer, in which T1 is ethylene or propylene, or a repeating structural part derived from a copolymer of an xcex1-olefin and alkyl acrylate or methacrylate,
q is a number from 2 to 100,
Q1 is xe2x80x94N(R41)xe2x80x94 or xe2x80x94Oxe2x80x94, in which R41 is as defined above,
in the formulae J and J*,
r is 1 or 2,
T7 has the meaning of R1 if n is 1 or 2 in the formula A,
in the formulae L and L*,
u is 1 or 2,
T13 has the meaning of R1 if n is 1 or 2 in the formula A, with the proviso that T13 is not hydrogen if u is 1,
in the formulae M and M*,
E1 and E2 are xe2x80x94COxe2x80x94 or xe2x80x94N(E5)xe2x80x94, in which E5 is hydrogen, C1-C12alkyl or C4xe2x80x94C22alkoxy-carbonylalkyl, where E1 and E2 have different meanings,
E3 is hydrogen, C1-C30alkyl, phenyl which is unsubstituted or substituted by chlorine or C1-C4alkyl, naphthyl which is unsubstituted or substituted by chlorine or C1-C4alkyl, or C7-C12phenylalkyl which is unsubstituted or substituted by C1-C4alkyl,
E4 is hydrogen, C1-C30alkyl, phenyl, naphthyl or C7-C12phenylalkyl, or
E3 and E4 together form a C4-C17polymethylene which is unsubstituted or substituted by one to four C1-C4alkyl radicals, in particular by methyl,
in the formulae N and N*,
R1 has the meaning of R1 in the formula A if n is 1,
G3 is the direct bond, C1-C12alkylene, phenylene or xe2x80x94NHxe2x80x94G1xe2x80x94NHxe2x80x94, in which G1 is C1-C12alkylene,
in the formulae O and O*,
R10 has the meaning of R10 in the formula C,
in the formulae P and P*,
E6 is an aliphatic or aromatic tetravalent radical, in particular neopentanetetrayl or benzenetetrayl,
in the formulae T and T*,
R51 is hydrogen, C1-C18alkyl, C5-C12cycloalkyl or C6-C10aryl,
R52 is hydrogen or C1-C18alkyl, or
R51 and R52 together are C4-C8alkylene,
f is 1 or 2,
if f is 1,
R50 has the meaning of R11 in the formula C if x is 1, or R50 is xe2x80x94(CH2)zCOOR54, in which z is a number from 1 to 4 and R54 is hydrogen or C1-C18alkyl, or R54 is a metal ion from the first, second or third group of the Periodic Table or is xe2x80x94N(R55)4, in which R55 is hydrogen, C1-C12alkyl or benzyl,
if f is 2,
R50 has the meaning of R11 in the formula C if x is 2,
in the formulae U and U*,
R53, R54, R55 and R56, independently of one another, are C1-C4alkyl or together form pentamethylene,
in the formulae V and V*,
R57, R58, R59 and R60, independently of one another, are C1-C4alkyl or together form pentamethylene,
in the formulae W and W*,
R61, R62, R63 and R64, independently of one another, are C1-C4alkyl, or together form pentamethylene,
R65 is C1-C5alkyl,
M is hydrogen or oxygen,
in which, in the formulae X to CC and X* to CC*,
n is from 2 to 3,
G1 is hydrogen, methyl, ethyl, butyl or benzyl,
m is a number from 1 to 4,
x is a number from 1 to 4,
if x is 1,
R1 and R2, independently of one another, are C1-C18 alkyl which is unsubstituted or substituted by one to five hydroxyl groups and which may be interrupted by one to five oxygen atoms, or C5-C12cycloalkyl, C7-C15aralkyl, C6-C10aryl which is unsubstituted or substituted by one to three C1-C8alkyl, or R1 is hydrogen, or R1 and R2 together are tetramethyl, pentamethylene, hexamethylene or 3-oxapentamethylene,
if x is 2,
R1 is hydrogen, C1-C8alkyl which is unsubstituted or substituted by hydroxyl and may be interrupted by one or two oxygen atoms,
R2 is C2-C18alkylene which is unsubstituted or substituted by one to five hydroxyl groups and may be interrupted by one to five oxygen atoms, o-, m- or p-phenylene which is unsubstituted or substituted by one or two C1-C4alkyl, or R2 is xe2x80x94(CH2)kO[(CH2)kO]h(CH2)kxe2x80x94, in which k is a number from 2 to 4 and h is a number 1 to 40, or
R1 and R2 together with the two N atoms to which they are bonded form piperazine-1,4-diyl,
if x is 3,
R1 is hydrogen,
R2 is C4-C8alkylene interrupted by a nitrogen atom,
if x is 4,
R1 is hydrogen,
R2 is C6-C12alkylene interrupted by two nitrogen atoms,
R3 is hydrogen, C1-C8alkyl which is unsubstituted or substituted by hydroxyl and may be interrupted by one or two oxygen atoms,
p is 2 or 3, and
Q is an alkali metal salt, ammonium or N+(G1)4 in which G1 is as defined above
and in the formulae DD and DD*
m is 2 or 3,
if m is 2,
G is xe2x80x94(CH2CHRxe2x80x94O)rCH2CHRxe2x80x94 in which or is a number from 0 to 3, and R is hydrogen or methyl and
if m is 3,
G is glyceryl,
in the formulae EE and EE*
G2 or is xe2x80x94CN, xe2x80x94CONH2 or xe2x80x94COOG3, in which G3 is hydrogen, C1-C18alkyl or phenyl,
X is an inorganic or organic anion,
where the total amount of the cations h corresponds to the total amount of the anions j; and
in which, in the formulae III to IIIc,
A11 is OR101 or NR111R112,
R101 is C2-C4alkenyl, propargyl, glycidyl, C2-C6alkyl which is unsubstituted or substituted by one to three hydroxyl groups and may be interrupted by one or two oxygen atoms, or R101 is C1-C4alkyl which is substituted by carboxyl or an alkali metal, ammonium or C1-C4alkylammonium salts, or R101 is alkyl which is substituted by xe2x80x94COOE10, in which E10 is methyl or ethyl, R102 is C3-C5alkyl which is interrupted by xe2x80x94COOxe2x80x94 or by xe2x80x94COxe2x80x94, or R102 is xe2x80x94CH2(OCH2CH2)cOCH3, in which c is a number from 1 to 4, or R102 is xe2x80x94NHR103, in which R103 is C1-C4alkyl,
a is a number from 2 to 4,
if a is 2,
T11 is xe2x80x94(CH2CHR100xe2x80x94O)dCH2CHR100xe2x80x94, in which d is 0 or 1, and R100 is hydrogen or methyl,
if a is 3,
T11 is glyceryl,
if a is 4,
T11 is neopentanetetrayl,
b is 2or 3,
if b is 2,
G11 is xe2x80x94(CH2CHR100xe2x80x94O)eCH2CHR100xe2x80x94, in which e is a number from 0 to 3 and R100 is hydrogen or methyl, and
if b is 3,
G11 is glyceryl,
R111 is hydrogen, C1-C4alkyl which is unsubstituted or substituted by one or two hydroxyl groups and may be interrupted by one or two oxygen atoms,
R112 is xe2x80x94COxe2x80x94R113, in which R113 has the meaning of R111 or R113 is xe2x80x94NHR114, in which R114 is C1-C4alkyl which is unsubstituted or substituted by one or two hydroxyl groups and/or by C1-C2-alkoxy, or R111 and R112 together are xe2x80x94COxe2x80x94CH2CH2xe2x80x94COxe2x80x94, xe2x80x94COxe2x80x94CHxe2x95x90CHxe2x80x94COxe2x80x94 or xe2x80x94(CH2)6xe2x80x94COxe2x80x94, with the proviso that if R113 is C1-C4alkyl, R111 is not hydrogen.
Important dye stabilizers for the process according to the invention are the compounds of the formulae A, A*, B, B*, C, C*, D, D*, Q, Q*, R, R*, S or S*, X, X*, Y, Y*, Z and Z*, in which E is oxyl or hydroxyl, and R is hydrogen,
in the formulae A and A*
n is 1 or 2,
if n is 1,
R1 is hydrogen, C1-C6alkyl, C2-C6alkenyl, propargyl, glycidyl, C2-C20alkyl which is unsubstituted or substituted by one to five hydroxyl groups and may be interrupted by one to ten oxygen atoms, or R1 is C1-C4alkyl which is substituted by carboxyl or xe2x80x94COOZ, in which Z is hydrogen or C1-C4alkyl,
if n is 2,
R1 is C1-C8alkylene, C4-C8alkenylene, C2-C20alkylene which is unsubstituted or substituted by one to five hydroxyl groups and may be interrupted by one to ten oxygen atoms,
in the formulae B and B*
m is 1 or 2,
if m is 1,
R2 is C1-C4alkyl, or R2 is CH2(OCH2CH2)nOCH3, in which n is a number from 1 to 12, or R2 is phenyl which is unsubstituted or substituted by one to three methyl groups, or R2 is xe2x80x94NHR3, in which R3 is C1-C4alkyl or phenyl which is unsubstituted or is substituted by one or two methyl groups,
if m is 2,
R is C1-C8alkylene, C4-C8alkenylene, or R2 is xe2x80x94CH2(OCH2CH2)nOCH2xe2x80x94, in which n is a number from 1 to 12,
R2 is NHR4NH, in which R4 is C2-C6alkyl, C8-C15aralkylene or C6-C12arylene, or R2 is xe2x80x94COxe2x80x94 or xe2x80x94NHCONH,
in the formulae C and C*,
R10 is hydrogen or C1-C3alkanoyl,
x is 1 or 2,
if x is 1,
R11 is hydrogen, C1-C6alkyl or glycidyl, or R11 is C1-C4alkyl which is substituted by carboxyl or COOZ, in which Z is hydrogen or C1-C4alkyl,
if x is 2,
R11 is C1-C6alkylene,
in the formulae D and D*,
R10 is hydrogen,
y is 1 or 2, and
R12 has the meaning given above for R2,
in the formulae Y, Y*, Z and Z*,
x is 1 or 2,
if x is 1,
R1 and R2, independently of one another, are C1-C4alkyl, or R1 and R2 together form tetramethylene or pentamethylene,
R2 is hydrogen or C1-C4alkyl substituted by hydroxyl,
if x is 2,
R1 is hydrogen, or C1-C4alkyl substituted by hydroxyl,
R2 is C2-C6alkylene, and
R3 is as defined above.
Particularly important dye stabilizers for the process according to the invention are the compounds of the formulae A, A*, B, B*, C, C*, D, D*, Q, Q*, R and R*, in which E is oxyl or hydroxyl and R is hydrogen,
in the formulae A and A*,
h is 1,
R1 is hydrogen, C1-C4alkyl, glycidyl, C2-C4alkyl which is unsubstituted or substituted by one or two hydroxyl groups and may be interrupted by one or two oxygen atoms, or R1 is C1xe2x80x944alkyl which is substituted by xe2x80x94COOZ, in which Z is hydrogen or C1-C4alkyl,
in the formulae B and B*,
m is 1 or 2,
R2 is C1-C4alkyl, or R2 is CH2(OCH2CH2)nOCH3, in which n is a number 1 to 4,
if m is 2,
R is C1-C8alkylene,
in the formulae C and C*,
R10 is hydrogen or C1-C2alkanoyl,
x is 1 or 2,
if x is 1,
R11 is hydrogen, C1-C4alkyl or glycidyl, or R11 is C1-C4alkyl which is substituted by xe2x80x94COOZ, in which Z is hydrogen or C1-C4alkyl,
if x is 2,
R11 is C1-C6alkylene,
in the formulae D and D*,
R10 is hydrogen,
y is 1 or 2, and
R12 has the meaning of R2.
Very particularly important dye stabilizers for the process according to the invention are the compounds:
(a) bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)sebacate;
(b) bis(1-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate;
(c) 1-hydroxy-2,2,6,6-tetramethyl-4-acetoxypiperidinium citrate;
(d) 1-oxyl-2,2,6,6-tetramethyl-4-acetamidopiperidine;
(e) 1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidine;
(f) 1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidinium bisulfate;
(g) 1-oxyl-2,2,6,6-tetramethyl-4-oxopiperidine;
(h) 1-hydroxy-2,2,6,6-tetramethyl-4-oxopiperidine;
(i) 1-hydroxy-2,2,6,6-tetramethyl-4-oxopiperidinium acetate;
(j) 1-oxyl-2,2,6,6-tetramethyl-4-methoxypiperidine;
(k) 1-hydroxy-2,2,6,6-tetramethyl-4-methoxypiperidine;
(l) 1-hydroxy-2,2,6,6-tetramethyl-4-methoxypiperidinium acetate;
(m) 1-oxyl-2,2,6,6-tetramethyl-4-acetoxypiperidine;
(n) 1-hydroxy-2,2,6,6-tetramethyl-4-acetoxypiperidine;
(o) 1-oxyl-2,2,6,6-tetramethyl-4-propoxypiperidine;
(p) 1-hydroxy-2,2,6,6-tetramethyl-4-propoxy-piperidinium acetate;
(q) 1-hydroxy-2,2,6,6-tetramethyl-4-propoxypiperidine;
(r) 1-oxyl-2,2,6,6-tetramethyl-4-(2-hydroxy-4-oxapentoxy)piperidine;
(s) 1-hydroxy-2,2,6,6-tetramethyl-4-(2-hydroxy-4-oxapentoxy)piperidinium acetate;
(t) 1-oxyl-2,2,6,6-tetramethyl-4-hydroxypiperidine;
(u) 1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidine;
(v) 1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium chloride;
(w) 1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium acetate;
(x) 1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium bisulfate;
(y) 1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium citrate;
(z) bis(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium)citrate;
(aa) tris(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium)citrate;
(bb) tetra(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium)ethylenediaminetetraacetate;
(cc) tetra(1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidinium)ethylenediaminetetraacetate;
(dd) tetra(1-hydroxy-2,2,6,6-tetramethyl-4-oxopiperidinium)ethylenediaminetetraacetate;
(ee) penta(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium)diethylenetriaminepentaacetate;
(ff) penta(1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidinium)diethylenetriaminepentaacetate;
(gg) penta(1-hydroxy-2,2,6,6-tetramethyl-4-oxopiperidinium)diethylenetriaminepentaacetate;
(hh) tri(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium)nitrilotriacetate;
(ii) tri(1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidinium)nitrilotriacetate;
(jj) tri(1-hydroxy-2,2,6,6-tetramethyl-4-oxopiperidinium)nitrilotriacetate;
(kk) penta(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium)diethylenetriaminepentamethylenephosphonate;
(ll) penta(1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidinium)diethylenetriaminepentamethylenephosphonate;
(mm) penta(1-hydroxy-2,2,6,6-tetramethyl-4-oxopiperidinium)diethylenetriaminepentamethylenephosphonate.
Preferred dye stabilizers in the process according to the invention are the compounds 1-oxyl-2,2,6,6-tetramethyl-4-hydroxypiperidine; 1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidine; 1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium chloride; 1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium acetate; 1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium bisulfate; 1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium citrate; bis(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium)citrate; tris(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium)citrate; tetra(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium)ethylenediaminetetraacetate; tetra(1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidinium)ethylenediaminetetraacetate; tetra(1-hydroxy-2,2,6,6-tetramethyl-4-oxopiperidinium)ethylenediaminetetraacetate; penta(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium)diethylenetriaminepentaacetate; penta(1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidinium)diethylenetriaminepentaacetate and penta(1-hydroxy-2,2,6,6-tetramethyl-4-oxopiperidinium)diethylenetriaminepentaacetate.
The dye stabilizer which is very particularly preferably used in the process according to the invention is the compound 1-oxyl-2,2,6,6-tetramethyl-4-hydroxypiperidine of the formula 
The compounds given above and used as dye stabilizers, and the preparation thereof are known, for example, from EP-A-0 943 665.
The present invention further provides for the use of the dye stabilizers of the formulae 
as compositions for protecting stained woods against the effect of light and heat, where G1, G2, Z1, Z2, E, X, h and j have the meanings and preferred meanings given above.
The dye stabilizers of the formula (I) or (II) are usually used in an amount of from 1 to 10% by weight, preferably 2 to 6% by weight, based on the weight of the wood to be treated.
Dyes which are suitable for use in the process according to the invention for the staining of wood are all customary dyes used in wood staining. In particular, acid dyes, and also cationic dyes, reactive dyes, and metal complex dyes are suitable for use in the process according to the invention.
Acid dyes are, for example, those dyes described in the Colour Index, 3rd edition (3rd revision 1987 including Additions and Amendments up to No. 85) under xe2x80x9cAcid Dyesxe2x80x9d. The anionic dyes which can be used may belong to a wide variety of dye classes and may contain one or more sulfonic acid groups. Examples are triphenylmethane dyes with at least two sulfonic acid groups, heavy-metal-free monoazo and disazo dyes each with one or more sulfonic acid groups and heavy-metal-containing, namely copper-, chromium-, nickel- or cobalt-containing monoazo, bisazo, azomethine and formazan dyes, in particular metallized dyes which contain two molecules of azo dye or one molecule of azo dye and one molecule of azomethine dye bonded to a metal atom, especially those which contain mono- and/or disazo dyes and/or azomethine dyes as ligands, and a chromium or cobalt ion as central atom, and also anthraquinone dyes, in particular 1-amino-4-arylaminoanthraquinone-2-sulfonic acids and 1,4-diarylamino- or 1-cycloalkylamino-4-arylaminoanthraquinonesulfonic acids.
Examples of cationic dyes are those dyes which are described in the Colour Index, 3rd edition, (3rd revision 1987 including additions and amendments up to No.85) under xe2x80x9cBasic Dyesxe2x80x9d. The cationic dyes which can be used may belong to a very wide variety of classes of dye. In particular, the cationic monoazo, anthraquinone and oxazine dyes are used in the process according to the invention.
Metal complex dyes are to be understood as meaning, for example, the metal-containing acid dyes described above under acid dyes, and also 1:1 or 1:2-metal complex dyes which do not have water-solubilizing groups, in particular do not have sulfo groups. Of the metal complex dyes, particular importance is given to the copper and cobalt complexes of azo, quinone oxime and hydroxyanthraquinone dyes.
The reactive dyes are, for example, those dyes described in the Colour Index, 3rd edition (3rd Revision 1987 including Additions and Amendments up to No.85) under xe2x80x9cReactive Dyesxe2x80x9d.
Examples of reactive dyes are dyes from the group of the monoazo, disazo, polyazo, metal complex azo, anthraquinone, phthalocyanine, formazan or dioxazine dyes which contain at least one reactive group. These dyes preferably also contain at least one sulfo group.
Reactive groups are understood as meaning radicals which are reactive towards fibres and which are able to react with the hydroxyl groups of cellulose, the amino, carboxyl, hydroxyl and mercapto groups of wool or silk, or with the amino or, where appropriate, the carboxyl groups of synthetic polyamides to form chemical covalent bonds. The reactive groups are usually joined to the dye radical directly or via a bridging element. Suitable reactive groups are, for example, those which have at least one substituent which can be detached from an aliphatic, aromatic or heterocyclic radical, or those in which the radicals have a radical suitable for reaction with the fibre material, for example a halogenotriazinyl, halogenopyrimidinyl or vinyl radical.
Of particular preference in the process according to the invention are the dyes of the formulae 
The dyes of the formulae (1) to (53) are known.
Very particular preference is given in the process according to the invention to the dyes of the formulae (1), (2), (3), (8), (12), (26), (27), (28), (29), (30), (31), (34), (42), (46), (48), (49), (50), (51), (52) and (53).
The present invention further provides an aqueous wood stain comprising at least one dye suitable for the staining of wood and at least one dye stabilizer of the formulae (I) or (II) 
where for G1, G2, Z1, Z2, E, X, h and j, and for the dyes used, the meanings and preferred meanings given above apply.
The wood stain according to the invention can also comprise further additives, for example UV absorbers, fungicides or insecticides. Examples of UV absorbers are the UV absorbers of the benzotriazole, 2-hydroxybenzophenone, 2-hydroxy-1,3,5-triazine and oxalanilide series. Examples of fungicides are 1-chloronaphthalene and pentachlorophenol. Examples of insecticides are DDT, cypermethrin, propiconazole and parathion.
Furthermore, the wood stain can comprise organic solvents, in particular glycols, polyglycols, ketones or glycol ethers, and especially alcohols.
Wood which can be stained and treated with the dye stabilizer used according to the invention is primarily to be understood as meaning shaped wooden bodies with extensive surfaces, for example wooden planks, plywood and chipboard, which may be veneered, carved wooden objects, and wooden sections glued, nailed or screwed together to give, for example, furniture, but also wood in finely divided form, for example wood chips or sawdust. Also suitable for the process according to the invention are thin wooden boards which are prepared by continuously shaving tree-trunks and which are joined together, e.g. glued together, only after they have been stained to give thicker boards or workpieces.
The treatment of the wood to be stained can be carried out, for example, by firstly staining the wood with a dye, optionally drying it and then treating it with a dye stabilizer of the formula (I) or (II), or by treating the wood to be stained directly with a wood stain comprising a dye and a dye stabilizer of the formula (I) or (II). The treatment of the stained wood with the dye stabilizer of the formula (I) or (II) can be carried out, for example, by treating the stained and optionally dried wood with an aqueous formulation of the dye stabilizer of the formula (I) or (II), or by incorporating the dye stabilizer of the formula (I) or (II) into a commercially available nitrocellulose lacquer with which the stained and optionally dried wood is then coated.
Depending on the nature and the type of wood, and the contact times of the wood stains comprising a dye stabilizer or a dye stabilizer and a dye, the dye can lie directly on the surface of the wood material or, advantageously, can penetrate deeper inside the wood.
The wood stain according to the invention is applied to the wood using customary methods, for example by immersing the wood in a bath of the wood stain, by paint-brushing, spraying or by knife-coating. The exposure time here can be up to several hours, and the temperature of the wood stain bath can generally be between 20 and about 110xc2x0 C. When the treatment is complete, the wooden objects are generally dried in the air at room temperature. The treated wood can, however, also be dried at elevated temperatures up to about 100xc2x0 C., e.g. in a convection drying cabinet.
The wood stain according to the invention can be used to treat all customary types of wood, for example pine, spruce, fir, oak, ash, beech, maple, walnut tree, pear tree, teak, mahogany, chestnut, birch tree, larch, hazelnut, lime tree, willow, poplar, elm, Scots pine, plane tree, obeche or aspen.
The examples below serve to illustrate the invention. Unless stated otherwise, the parts are parts by weight and the percentages are percentages by weight. The temperatures are given in degrees Celsius. The relationship between parts by weight and parts by volume is the same as that between grams and cubic centimetres.